The conventional technical method of producing organolithium compounds (Kirk-Othmer, "Enc. Chem. Techn.", Vol 12, p. 547, 1967) is based on the reaction of lithium metal with organic halogen compounds, in which organolithium compounds as well as lithium halides are produced: EQU RX+2Li.fwdarw.RLi+LiX (1)
X=Cl, Br, I PA1 R=allyl, benzyl PA1 R'=phenyl, mesitoyl PA1 X=Cl, Br, I PA1 G is a carbon atom bonded to a radicl R.sup.1 PA1 D is a carbon atom bonded to a radical R.sup.2 and there is a double bond between the carbon atom of G and of D; PA1 E is carbon PA1 F is oxygen, sulfur, ##STR2## Me is an alkali metal n is an integer from 2 to 20; PA1 L and L' are mono or poly-functional ethers or amines; PA1 p and q are integers from 0 to 4; PA1 R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently hydrogen, alkyl, cycloalkyl, aralkyl or aryl groups PA1 R.sup.1 =R.sup.4 is C.sub.6 H.sub.5, and PA1 R.sup.2 =R.sup.3 is hydrogen and PA1 Me is lithium and PA1 R.sup.1 =R.sup.3 is C.sub.6 H.sub.5, PA1 R.sup.2 =R.sup.4 is hydrogen and PA1 Me is lithium, and PA1 zinc chloride, PA1 iron (III) chloride PA1 copper (I) chloride PA1 copper (II) chloride PA1 molybdenum (VI) chloride PA1 titanium (IV) chloride PA1 chromium (III) chloride PA1 molybdenum (V) chloride PA1 managanese (II) chloride PA1 cobalt (II) chloride PA1 nickel (II) chloride PA1 nickel (II) acetylacetonate PA1 rhodium (III) chloride PA1 platinum (II) chloride PA1 palladium (II) chloride PA1 a polycyclic aromatic compound; PA1 an alkali metal; and PA1 a metal compound of transition metals from group Ib, IIb, IVb, Vb, VIb, VIIb and VIIIb of the periodic system. PA1 naphthalene, PA1 anthracene, PA1 phenanthrene, and PA1 diphenyl PA1 G is carbon bonded to a radical R.sub.1 PA1 D is carbon bonded to a radical R.sub.2, and, if A and B are oxygen, also to a hydrogen atom, PA1 E is carbon, PA1 F is a member of the group consisting of oxygen, sulfur, hydroxy where B is oxygen, ##STR7## R.sup.1, R.sup.2, R.sup.3, R.sup.4 represent hydrogen, alkyl, cycloalkyl, aralkyl or aryl groups and/or two or more of such groups are closed into an aliphatic or aromatic ring system, and PA1 M* represents a metal compound of metals from groups Ib, IIb, IVb, Vb, VIb, VIIb, and VIIIb or the periodic system and/or a group Me.sub.n (L).sub.p (L').sub.q wherein Me is an alkali metal PA1 n is an integer from 2 to 20; PA1 L and L' are monofunctional or polyfunctional ethers or amines, and PA1 p and q are integers from 0 to 4; PA1 R'=R.sup.4 is phenyl, PA1 R.sup.2 =R.sup.3 is hydrogen and PA1 Me is lithium, and PA1 R.sup.1 =R.sup.3 is phenyl PA1 R.sup.2 =R.sup.4 is hydrogen, and PA1 Me is lithium, and PA1 zinc chloride, PA1 iron (III) chloride, PA1 copper (I) chloride, PA1 copper (II) chloride, PA1 molybdenum (VI) chloride, PA1 titanium (IV) chloride, PA1 chromium (III) chloride, PA1 molybdenum (V) chloride, PA1 manganese (II) chloride, PA1 cobalt (II) chloride, PA1 nickel (II) chloride, PA1 nickel (II) acetylacetonate, PA1 rhodium (III) chloride, PA1 platinum (II) chloride and PA1 palladium (II) chloride. PA1 G is a carbon atom bonded to a radical R.sub.1 PA1 D is a carbon atom bonded to a radical R.sub.2 and there is a double bond between the carbon atom of G and of D. PA1 E is carbon PA1 F is oxygen sulfur, ##STR17## R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently hydrogen, alkyl, cycloalkyl, aralkyl or aryl groups and/or two or more of such groups are closed into an aliphatic or aromatic ring system; PA1 an alkali metal; and PA1 mono or poly-functional ethers or amines. PA1 X is sulfur or oxygen; PA1 n is an integer from 2 to 20; PA1 L and L' are monofunctional or polyfunctional ethers or amines; PA1 p and q are integers from 0 to 4; PA1 R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are hydrogen, alkyl, cycloalkyl, aralkyl or aryl groups; and/or where two or more of such groups are closed into an aliphatic or aromatic ring system; or PA1 (d) a metal compound of transition metals of group 1B, IIb, IVb, Vb, VIb, VIIb, and VIIIb of the periodic system.
Allyllithium and benzyllithium compounds may among others be produced by the splitting of the corresponding ether derivative or acyloxy derivative with lithium metal (J. A. Katzen-ellenbogen R. S. Lenox, J. Org. Chem., 38, 326, 1973; U. Schollkopf in "Methoden der Organischen Chemie", Houben-Weyl, XIII/1, P. 161; J. J. Eisch, A. M. Jacobs, J. Org. Chem. 28, 2145 1963): EQU ROR'+2Li.fwdarw.R-Li+R'OLi (2)
From the organolithium compounds so produced, numerous other organolithium compounds may be obtained by means of metal-H exchange: EQU R-Li+R'H.fwdarw.R--H+R'--Li (3)
or by means of metal-halogen exchange (D. Seebach. K.-H. Geiss in "New Applications of Organometallic Reagents in Organic Synthesis", p. 1, Elsevier, 1976): EQU R-Li+R'--X.fwdarw.R'--Li+R--X (4)
Only in exceptional cases had it heretofore been possible to synthesize organolithium compounds directly from lithium metal and hydrocarbons. Thus, for instance, 1-alkines (H. Ogura, H. Takashi, Synth. Commun., 3 135, 1973), triphenylmethane or acenaphtylene (B. J. Wakefield, "The Chemistry of Organolithium Compounds", p. 70, Pergamon Press, 1974) may be lithiated with metallic lithium. According to D. L. Skinner et al (J. Org. Chem., 32, 105, 1967) lithium reacts with 1-alkenes in the absence of a solvent to produce 1-alkinyllithium compounds and lithium hydride.: EQU RCH=CH.sub.2 +4 Li.fwdarw.RC.tbd.C--Li+3 LiH (5)
whereby 1-lithio-1-alkenes are produced as byproducts of the reaction, at very small yields. In the presence of tetrahydrofuran (THF) 1-lithio-1-hexene was obtained from lithium and 1-hexene at boiling temperatures, at 9% yield.
A procedure for the preparation of organolithium compounds from lithium and ethylene in dimethoxymethane or THF in the presence of biphenyl and, if the case, naphthalene was recently made known (V. Rautenstrauch of Firmenich S.A., Geneva, Swiss Patent No. 585, 760, May 20, 1974; V. Rautenstrauch, Angew, Chem., 87, 254, 1975). The yields of organolithium compounds according to these procedures are at very low levels. Since the reaction products furthermore occur in the form of a mixture of vinyl-lithium and 1,4-dilithiobutane, this procedure hardly seems suitable for technical purposes.